Thermal annealing process

ABSTRACT

A method for processing a substrate is provided; wherein the method comprises applying a film of a copolymer composition, comprising a poly(styrene)-b-poly(dimethylsiloxane) block copolymer component to a surface of the substrate; optionally, baking the film; subjecting the film to a high temperature annealing process under particularized atmospheric conditions for a specified period of time; followed by a treatment of the annealed film to remove the poly(styrene) from the annealed film and to convert the poly(dimethylsiloxane) in the annealed film to SiO x .

The present invention relates to the field of self assembling block copolymers. In particular, the present invention is directed to a specific thermal annealing process for poly(styrene)-b-poly(dimethylsiloxane) block copolymer film compositions deposited onto the surface of a substrate.

Some block copolymers, consisting of two or more distinct homopolymers joined end to end, are known to self-assemble into periodic micro domains having typical dimensions of 10 nanometers to 50 nanometers (nm). The possibility of using such micro domains to pattern surfaces has attracted increasing interest because of the expense and difficulty of patterning in nanoscale dimensions (especially sub-45 nm) using optical lithography.

Controlling the lateral placement of the block copolymer micro domains on the substrates continues to be a challenge, however. This problem has been previously addressed using lithographically pre-defined topographic and/or chemical patterning of the substrate. Previous studies have demonstrated that self-assembled block copolymer micro domains in form of lamellae can be directed to follow chemical patterning of the substrate, yielding periodicities close to those of the chemical pre-patterns. Other studies have shown that by controlling the surface wetting properties of the block copolymer on the bottom and side walls of a topographic pre-pattern, the lamellae can be directed to follow the topographic pre-pattern. The lamellae formed line/space patterns of smaller dimensions than the substrate pre-pattern, subdividing the topographic pre-pattern into a higher frequency line pattern; that is, a line pattern having a smaller pitch. One limitation of block copolymer patterning is the propensity of the patterns to form everywhere on the pre-pattern surface, for topographic and/or chemical guiding pre-patterns.

The ability to shrink the size of various features on a given substrate (e.g., gates in field effect transistors) is currently limited by the wavelength of light used to expose photoresists (i.e., 193 nm). These limitations create a significant challenge for the fabrication of features having a critical dimension (CD) of <50 nm. The use of conventional block copolymers present difficulties in orientation control and long range ordering during the self assembly process. Moreover, such block copolymers frequently provide inadequate etch resistance for subsequent processing steps.

Diblock copolymers of poly(styrene) and poly(dimethylsiloxane) offer promise for application in the patterning of nanoscale dimensions (especially sub-45 nm) using directed self assembly techniques. Conventional wisdom in the art; however, is that the use of poly(styrene)-b-poly(dimethylsiloxane) block copolymers in such operations cannot effectively be thermally annealed. Accordingly, those in the art have developed a variety of alternative techniques for processing poly(styrene)-b-poly(dimethylsiloxane) block copolymers.

For example, in U.S. Patent Publication No. 2011/0272381; Millward, et al., disclose a solvent annealing method for processing diblock copolymer films such as poly(styrene)-b-poly(dimethylsiloxane).

Notwithstanding, there remains a need for alternative methods of processing poly(styrene)-b-poly(dimethylsiloxane) diblock copolymer compositions for use in directed self assembly applications.

The present invention provides a method for processing a substrate, comprising: providing a substrate having a surface; providing a copolymer composition, comprising a poly(styrene)-b-poly(dimethylsiloxane) block copolymer component, wherein the number average molecular weight of the poly(styrene)-b-poly(dimethylsiloxane) block copolymer component is 25 to 1,000 kg/mol; applying a film of the copolymer composition to the surface of the substrate; optionally, baking the film; heating the film at 275 to 350° C. under a gaseous atmosphere having an oxygen concentration of ≦7.5 ppm for a period of 1 second to 4 hours; and, treating the annealed film to remove the poly(styrene) from the annealed film and to convert the poly(dimethylsiloxane) in the annealed film to SiO_(x).

The present invention provides a method for processing a substrate, comprising: providing a substrate having a surface; providing a copolymer composition, comprising a poly(styrene)-b-poly(dimethylsiloxane) block copolymer component, wherein the poly(styrene)-b-poly(dimethylsiloxane) block copolymer component provided is a single poly(styrene)-b-poly(dimethylsiloxane) diblock copolymer having a number average molecular weight, M_(N), of 25 to 1,000 kg/mol; a polydispersity, PD, of 1 to 3; and a poly(dimethylsiloxane) weight fraction, Wf_(PDMS), of 0.19 to 0.33; applying a film of the copolymer composition to the surface of the substrate; optionally, baking the film; heating the film at 275 to 350° C. under a gaseous atmosphere having an oxygen concentration of ≦7.5 ppm for a period of 1 second to 4 hours; and, treating the annealed film to remove the poly(styrene) from the annealed film and to convert the poly(dimethylsiloxane) in the annealed film to SiO_(x).

The present invention provides a method for processing a substrate, comprising: providing a substrate having a surface; providing a copolymer composition, comprising a poly(styrene)-b-poly(dimethylsiloxane) block copolymer component, wherein the poly(styrene)-b-poly(dimethylsiloxane) block copolymer component is a blend of at least two different poly(styrene)-b-poly(dimethylsiloxane) block copolymers; wherein the at least two different poly(styrene)-b-poly(dimethylsiloxane) block copolymers are selected from the group of poly(styrene)-b-poly(dimethylsiloxane) block copolymers having a number average molecular weight, M_(N), of 1 to 1,000 kg/mol and a polydispersity, PD, of 1 to 3; and, wherein the blend exhibits a blend number average molecular weight, M_(N-Blend), of 25 to 1,000 kg/mol; applying a film of the copolymer composition to the surface of the substrate; optionally, baking the film; heating the film at 275 to 350° C. under a gaseous atmosphere having an oxygen concentration of ≦7.5 ppm for a period of 1 second to 4 hours; and, treating the annealed film to remove the poly(styrene) from the annealed film and to convert the poly(dimethylsiloxane) in the annealed film to SiO_(x).

The present invention provides a method for processing a substrate, comprising: providing a substrate having a surface; providing a copolymer composition, comprising a poly(styrene)-b-poly(dimethylsiloxane) block copolymer component, wherein the poly(styrene)-b-poly(dimethylsiloxane) block copolymer component is a blend of at least two different poly(styrene)-b-poly(dimethylsiloxane) block copolymers; wherein the at least two different poly(styrene)-b-poly(dimethylsiloxane) block copolymers are selected from the group of poly(styrene)-b-poly(dimethylsiloxane) block copolymers having a number average molecular weight, M_(N), of 1 to 1,000 kg/mol and a polydispersity, PD, of 1 to 3; wherein the blend exhibits a blend number average molecular weight, M_(N-Blend), of 25 to 1,000 kg/mol; and, wherein the blend exhibits a blend poly(dimethylsiloxane) weight fraction, Wf_(PDMS-Blend), of 0.19 to 0.33; applying a film of the copolymer composition to the surface of the substrate; optionally, baking the film; heating the film at 275 to 350° C. under a gaseous atmosphere having an oxygen concentration of ≦7.5 ppm for a period of 1 second to 4 hours; and, treating the annealed film to remove the poly(styrene) from the annealed film and to convert the poly(dimethylsiloxane) in the annealed film to SiO_(x).

The present invention provides substrates that have been processed according to the method of the present invention, wherein a surface of the substrate comprises sublithographic SiO_(x) features.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a depiction of a top down scanning electron microscopic (“SEM”) image of the product film prepared according to Comparative Example F1.

FIG. 2 is a depiction of a top down scanning electron microscopic (“SEM”) image of the product film prepared according to Example 10.

FIG. 3 is a depiction of a top down scanning electron microscopic (“SEM”) image of the product film prepared according to Comparative Example F2.

FIG. 4 is a depiction of a top down scanning electron microscopic (“SEM”) image of the product film prepared according to Example 11.

DETAILED DESCRIPTION

The present invention provides a method for forming lithographically useful line and space features used in the subsequent pattern transfer processing in the construction of devices requiring microscopic etching or micropatterned surfaces (e.g., microelectronics, microsensors and biochips). The method of the invention provides for the creation of patterns having pitch dimensions divisible by an integer factor relative to a guiding pattern created on a substrate using conventional lithographic means. The ability to form such highly resolved patterns with smaller dimensions, for example, one half or one fourth that which can be produced using conventional lithographic techniques enables, for example, entire new technologies in the design and manufacture of semiconductor chips.

The term “PS-b-PDMS block copolymer” used herein and in the appended claims is short hand for a poly(styrene)-block-poly(dimethylsiloxane) diblock copolymer.

The term “M_(N)” used herein and in the appended claims in reference to a block copolymer of the present invention is the number average molecular weight of the block copolymer (in g/mol) determined according to the method used herein in the Examples.

The term “M_(N-Blend) or blend number average molecular weight” used herein and in the appended claims in reference to a PS-b-PDMS blend used in the copolymer composition of the present invention is the weighted average of the number average molecular weights of the PS-b-PDMS block copolymers included in the PS-b-PDMS blend.

The term “M_(w)” used herein and in the appended claims in reference to a block copolymer of the present invention is the weight average molecular weight of the block copolymer (in g/mol) determined according to the method used herein in the Examples.

The term “M_(W-blend) or blend weight average molecular weight” used herein and in the appended claims in reference to a PS-b-PDMS blend used in the copolymer composition of the present invention is the weighted average of the weight average molecular weights of the PS-b-PDMS block copolymers included in the PS-b-PDMS blend.

The term “PD” used herein and in the appended claims in reference to a block copolymer of the present invention is the polydispersity of the block copolymer determined according to the following equation:

${PD} = {\frac{M_{W}}{M_{N}}.}$

The term “average molecular weight” used herein and in the appended claims in reference to (a) a PS-b-PDMS block copolymer component that is a single PS-b-PDMS block copolymer, means the number average molecular weight, M_(N), for that PS-b-PDMS block copolymer; and (b) a PS-b-PDMS block copolymer component that is a blend of two or more different PS-b-PDMS block copolymers, means the weighted average of the number average molecular weights, M_(N), of the two or more different PS-b-PDMS block copolymers in the blend.

The term “Wf_(PS)” used herein and in the appended claims in reference to a PS-b-PDMS block copolymer is the weight percent of the poly(styrene) block in the block copolymer.

The term “Wf_(PS-Blend) or blend poly(styrene) weight fraction” used herein and in the appended claims in reference to a PS-b-PDMS blend used in the copolymer composition of the present invention is the weighted average of the weight percent of the poly(styrene) block in the PS-b-PDMS block copolymers included in the PS-b-PDMS blend.

The term “Wf_(PDMS)” used herein and in the appended claims in reference to a PS-b-PDMS block copolymer of the present invention is the weight percent of the poly(dimethylsiloxane) block in the block copolymer.

The term “Wf_(PDMS-Blend) or blend poly(dimethylsiloxane) weight fraction” used herein and in the appended claims in reference to a PS-b-PDMS blend used in the copolymer composition of the present invention is the weighted average of the weight percent of the poly(dimethylsiloxane) block in the PS-b-PDMS block copolymers included in the PS-b-PDMS blend.

Block copolymers are polymers that are synthesized from two or more different monomers and exhibit two or more polymeric chain segments that are chemically different, but yet, are covalently bound to one another. Diblock copolymers are a special class of block copolymers derived from two different monomers (e.g., A and B) and having a structure comprising a polymeric block of A residues covalently bound to a polymeric block of B residues (e.g., AAAAA-BBBBB).

The copolymer composition used in the method of the present invention, comprises a poly(styrene)-b-poly(dimethylsiloxane) block copolymer component, wherein the poly(styrene)-b-poly(dimethylsiloxane) block copolymer component is selected from the group consisting of (a) a single PS-b-PDMS block copolymer; and, (b) a blend of at least two different PS-b-PDMS block copolymers.

When the poly(styrene)-b-poly(dimethylsiloxane) block copolymer component used in the method of the present invention is a single PS-b-PDMS block copolymer, the PS-b-PDMS block copolymer used preferably exhibits a number average molecular weight, M_(N), of 25 to 1,000 kg/mol (preferably 30 to 1,000 kg/mol; more preferably 30 to 100 kg/mol; most preferably 30 to 60 kg/mol); a polydispersity, PD, of 1 to 3 (preferably 1 to 2; most preferably 1 to 1.2); and, a poly(dimethylsiloxane) weight fraction, Wf_(PDMS), of 0.19 to 0.33 (preferably 0.21 to 0.28; most preferably 0.22 to 0.25). Given the teachings provided herein, one of ordinary skill in the art will be able to deposit such a copolymer composition comprising a single PS-b-PDMS block copolymer using the method of the present invention, wherein cylindrical poly(dimethylsiloxane) domains in the deposited copolymer composition will self assemble to orient themselves with their axes of symmetry parallel to the surface of the substrate, perpendicular to the surface of the substrate or a combination of parallel and perpendicular to the surface of the substrate, through the selection and control of the film deposition conditions, for example: (a) the substrate's surface energy (i.e., by pretreating the surface of the substrate with an interposing material), (b) the thickness of the film of copolymer composition deposited, (c) the bake profile of the deposited copolymer composition (i.e., bake temperature and bake time) and (d) the anneal profile of the deposited copolymer composition (i.e., anneal temperature and anneal time).

When the poly(styrene)-b-poly(dimethylsiloxane) block copolymer component used in the method of the present invention is a blend of at least two different PS-b-PDMS block copolymers, the at least two different PS-b-PDMS block copolymers are preferably selected from the group of PS-b-PDMS block copolymers having a number average molecular weight, M_(N), of 1 to 1,000 kg/mol (preferably 1 to 100 kg/mol; most preferably 5 to 60 kg/mol); and a polydispersity, PD, of 1 to 3 (preferably 1 to 2; most preferably 1 to 1.2). The blend of at least two different PS-b-PDMS block copolymers used preferably exhibits a blend number average molecular weight, M_(N-Blend), of 25 to 1,000 kg/mol (preferably 30 to 1,000 kg/mol; more preferably 30 to 100; most preferably 30 to 60 kg/mol). The blend of at least two different PS-b-PDMS block copolymers used preferably exhibits a blend poly(dimethylsiloxane) weight fraction, Wf_(PDMS-Blend), of 0.19 to 0.33 (preferably 0.21 to 0.28; most preferably 0.22 to 0.25). Preferred poly(styrene)-b-poly(dimethylsiloxane) block copolymer components comprise a blend of at least two different PS-b-PDMS block copolymers. When compared on an equivalent molecular weight (i.e., M_(N-single PS-b-PDMS)=M_(N-Blend)) and an equivalent poly(dimethylsiloxane) weight fraction (i.e., Wf_(PDMS-single PS-b-PDMS)=Wf_(PDMS-Blend)) basis, the copolymer compositions comprising a blend of PS-b-PDMS block copolymers provide significant value over single PS-b-PDMS block copolymer compositions in that the blend systems tend to exhibit faster annealing profiles and lower defectivity (compared on an equivalent molecular weight/PDMS weight fraction basis in directed self assembly applications used to form periodic nanostructures, such as line/space patterns on silicon containing substrates. Given the teachings provided herein, one of ordinary skill in the art will be able to deposit such a copolymer composition comprising a blend of PS-b-PDMS block copolymers using the method of the present invention, wherein cylindrical poly(dimethylsiloxane) domains in the deposited copolymer composition will self assemble to orient themselves with their axes of symmetry parallel to the surface of the substrate, perpendicular to the surface of the substrate or a combination of parallel and perpendicular to the surface of the substrate, through the selection and control of the film deposition conditions, for example: (a) the substrate's surface energy (i.e., by pretreating the surface of the substrate with an interposing material), (b) the thickness of the film of copolymer composition deposited, (c) the bake profile of the deposited copolymer composition (i.e., bake temperature and bake time) and (d) the anneal profile of the deposited copolymer composition (i.e., anneal temperature and anneal time).

The copolymer composition used in the method of the present invention, optionally further comprises a solvent. Solvents suitable for use in copolymer composition include liquids that are able to disperse the poly(styrene)-b-poly(dimethylsiloxane) block copolymer component into particles or aggregates having an average hydrodynamic diameter of less than 50 nm as measured by dynamic light scattering. Preferably, the solvent used is selected from propylene glycol monomethyl ether acetate (PGMEA), ethoxyethyl propionate, anisole, ethyl lactate, 2-heptanone, cyclohexanone, amyl acetate, γ-butyrolactone (GBL), n-methylpyrrolidone (NMP) and toluene. More preferably, the solvent used is selected from propylene glycol monomethyl ether acetate (PGMEA) and toluene. Most preferably, the solvent used is toluene.

The copolymer composition used in the method of the present invention, optionally further comprises an additive. Additives include additional polymers (including homopolymers and random copolymers); surfactants; antioxidants; photoacid generators; thermal acid generators; quenchers; hardeners; adhesion promoters; dissolution rate modifiers; photocuring agents; photosensitizers; acid amplifiers; plasticizers; orientation control agents; and cross linking agents. Preferred additives for use in the copolymer composition of the present invention include surfactants and antioxidants.

Substrates used include any substrate having a surface that can be coated with the copolymer composition in the method of the present invention. Preferred substrates include layered substrates. Preferred substrates include silicon containing substrates (e.g., glass; silicon dioxide; silicon nitride; silicon oxynitride; silicon containing semiconductor substrates such as silicon wafers, silicon wafer fragments, silicon on insulator substrates, silicon on sapphire substrates, epitaxial layers of silicon on a base semiconductor foundation, silicon-germanium substrates); plastic; metals (e.g., copper, ruthenium, gold, platinum, aluminum, titanium and alloys); titanium nitride; and non-silicon containing semiconductive substrates (e.g., non-silicon containing wafer fragments, non-silicon containing wafers, germanium, gallium arsenide and indium phosphide). Most preferred substrates are silicon containing substrates.

Optionally, in the method of the present invention, the surface of the substrate to be coated with the copolymer composition is pretreated with an interposing material before the copolymer composition is applied. Preferably, the pretreatment material acts like a tying layer interposed between the surface of the substrate and the copolymer composition to enhance the adhesion between the poly(styrene)-b-poly(dimethylsiloxane) block copolymer component and the substrate. Preferably, the interposing material forms a layer selected from an imaging layer and an orientation control layer.

Imaging layers suitable for use in the method of the present invention include, for example, any type of material that can be patterned or selectively activated. Such materials include, for example, polymer brushes and a self-assembled monolayers of silane and siloxane compounds.

Orientation control layers suitable for use in the method of the present invention include neutral and non-neutral orientation control layers. That is, the orientation control layer can form an interface between the surface of the substrate and copolymer composition that is preferentially wetted by one of poly(styrene) or poly(dimethylsiloxane)—i.e., a non-neutral orientation control layer. A neutral orientation control layer refers to a layer that forms an interface between the surface of the substrate and the copolymer composition that is equally wetted by both poly(styrene) and poly(dimethylsiloxane).

Preferably, the substrate is pretreated in the method of the present invention before depositing the copolymer composition to facilitate the guided self assembly of the poly(styrene)-b-poly(dimethylsiloxane) block copolymer component in the copolymer composition. Specifically, the pretreatment can facilitate one of the two conventional methods used for guided self assembly of block copolymer films, namely graphoepitaxy and chemical epitaxy. In the graphoepitaxy, the surface of the substrate is prepatterned with topographical features on the surface of substrate (e.g., trenches, holes) that operate to direct the self organization of the poly(styrene) and the poly(dimethylsiloxane) blocks in the poly(styrene)-b-poly(dimethylsiloxane) block copolymer component of the copolymer composition.

In the chemical epitaxy, the surface of the substrate is treated with a film that exhibits a compositional pattern, wherein the affinity between the various parts of the compositional pattern is different for poly(styrene) and poly(dimethylsiloxane). This chemical affinity difference operates to facilitate the directed self assembly of the poly(styrene)-b-poly(dimethylsiloxane) block copolymer component of the copolymer composition.

Preferably, in the method of the present invention, the interposing layer is formed on the substrate using a method selected from spin coating, dip coating, roll coating, spray coating and laminating (most preferably spin coating). After application of the interposing layer forming material onto the surface of the substrate, the material is optionally further processed to remove any residual solvent. Preferably, the interposing layer is baked at an elevated temperature (e.g., 70 to 340° C.) for at least 10 seconds to 5 minutes to remove any residual solvent from the interposing layer. Preferably, the baked interposing layer is rinsed with a solvent capable of removing any residual unbound interposing layer material from the surface of the substrate and then rebaked at an elevated temperature (e.g., 70 to 340° C.) for at least 10 seconds to 5 minutes to remove any residual solvent.

Applying a film of the copolymer composition comprising the poly(styrene)-b-poly(dimethylsiloxane) block copolymer component to the surface of the substrate in the method of the present invention preferably comprises depositing the copolymer composition onto the surface of the substrate using a method selected from spin coating, dip coating, roll coating, spray coating and laminating (most preferably spin coating). After application of a film of the copolymer composition to the substrate, the film is optionally further processed to remove any residual solvent. Preferably, the film is baked at an elevated temperature (e.g., 70 to 340° C.) for at least 10 seconds to 5 minutes to remove any residual solvent from the deposited copolymer composition.

In the method of the present invention, the deposited film of the copolymer composition is then thermally annealed by heating the film at a temperature of 275 to 300° C. (preferably 300 to 350° C.; most preferably 320 to 350° C.) under a gaseous atmosphere having an oxygen concentration of ≦7.5 ppm (preferably ≦6.5; more preferably ≦4 ppm) for a period of 1 second to 4 hours (preferably 2 seconds to 1 hour; more preferably 30 seconds to 1 hour; most preferably 90 seconds to 1 hour) to enable the poly(styrene)-b-poly(dimethylsiloxane) block copolymer component to self assemble on the surface of the substrate. Preferably, the deposited film is annealed under a gaseous atmosphere selected from nitrogen and argon, wherein the gaseous atmosphere has an oxygen concentration of ≦6.5 (more preferably <4 ppm). Most preferably, the deposited film is annealed under a gaseous nitrogen atmosphere having an oxygen concentration of ≦4 ppm.

In the method of the present invention, the annealed film is treated to remove the poly(styrene) in the annealed film and to convert the poly(dimethylsiloxane) in the annealed film to SiO_(x), providing a product film with a plurality of voids (e.g., trenches perpendicular to the surface of the substrate; or a plurality of cylindrical SiO_(x) posts with axes of symmetry perpendicular to the surface of the substrate). The treatment comprises: exposing the film to conditions that exhibit differential reactivity towards the poly(styrene) in the film relative to the poly(dimethylsiloxane) in the film, to facilitate removal of the poly(styrene) domains from the annealed film and the conversion of the poly(dimethylsiloxane) domains to SiO_(x). Preferably, the treatment comprises: optionally, exposing the annealed film to a halogen containing plasma (e.g., CF₄) to remove any wetting layer that formed on the surface of the annealed film; followed by exposing the annealed film to a reactive plasma or a reactive ion etching atmosphere to remove the poly(styrene) and to convert the poly(dimethylsiloxane) to SiO_(x). Most preferably, the treatment comprises: exposing the annealed film to a halogen containing plasma to remove any wetting layer formed on the annealed film; and then exposing the annealed film to a reactive plasma or a reactive ion etching atmosphere, wherein the atmosphere comprises a plasma composed of a low pressure ionized oxidizing gas (preferably O₂); wherein the poly(styrene) in the annealed film is removed and the poly(dimethylsiloxane) in the annealed film is converted to SiO_(x).

Some embodiments of the present invention will now be described in detail in the following Examples.

The following materials were passed through a column packed with activated A-2 grade alumina before being used in the Examples herein, namely tetrahydrofuran (99.9% pure available from Aldrich), styrene (available from Aldrich), and cyclohexane (HPLC grade available from Fischer). All the other materials used in the Examples herein were commercial materials that were used as received.

The film thicknesses reported in the Examples herein were measured using a NanoSpec/AFT 2100 Film Thickness Measurement tool. The thickness of the films were determined from the interference of a white light passed through a diffraction grating. A standard program called “Polyimide on Silicon” was used to analyze the component wavelengths (380-780 nm) to determine the film thickness. The thickness of the poly(styrene)-b-poly(dimethylsiloxane) block copolymer composition and the brush layer were measured together as one polymer layer. The reported film thickness is the combined thickness of the block copolymer composition and the brush layer.

The number average molecular weight, M_(N), and polydispersity values reported in the Examples were measured by gel permeation chromatography (GPC) on an Agilent 1100 series LC system equipped with an Agilent 1100 series refractive index and MiniDAWN light scattering detector (Wyatt Technology Co.). Samples were dissolved in HPLC grade tetrahydrofuran (THF) at a concentration of approximately 1 mg/mL and filtered through at 0.20 μm syringe filter before injection through the two PLGel 300×7.5 mm Mixed C columns (5 mm, Polymer Laboratories, Inc.). A flow rate of 1 mL/min and temperature of 35° C. were maintained. The columns were calibrated with narrow molecular weight PS standards (EasiCal PS-2, Polymer Laboratories, Inc.).

Proton nuclear magnetic resonance (¹H NMR) spectroscopy results referred to in the Examples was done on a Varian INOVA 400 MHz NMR spectrometer. Deuterated tetrahydrofuran, THF, was used. A delay time of 10 seconds was used to ensure complete relaxation of protons for quantitative integrations. Chemical shifts are reported relative to tetramethylsilane.

Example 1 Preparation of Hydroxyl-Terminated Polystyrene Brush

Into a 2 liter glass reactor under a nitrogen atmosphere was added cyclohexane (1,500 g). Styrene (50.34 g) was then added to the reactor via cannula. The contents of the reactor were then heated to 40° C. Sec-butyllithium (19.18 g) diluted in cyclohexane to a concentration of 0.32 M was then rapidly added to the reactor via cannula, causing the reactor contents to turn yellow. The contents of the reactor were stirred for 30 minutes. The contents of the reactor were then cooled to 30° C. Ethylene oxide (0.73 g) was then transferred into the reactor. The contents of the reactor were stirred for 15 minutes. Then a 20 mL of a 1.4 M solution of HCl in methanol was added to the reactor. The polymer in the reactor was then isolated by precipitating into isopropanol at a ratio of 500 mL of polymer solution to 1,250 mL of isopropanol. The resulting precipitate was then filtered and dried overnight in a vacuum oven at 60° C., yielding 42 g of product hydroxyl-terminated polystyrene brush. The product hydroxyl-terminated polystyrene brush exhibited a number average molecular weight, M_(N), of 7.4 kg/mol and a polydispersity, PD, of 1.07.

Example 2 Preparation of PS-b-PDMS Diblock Copolymer

Into a 500 mL round bottom reactor under an argon atmosphere was added cyclohexane (56 g) and styrene (16.46 g). The contents of the reactor were then warmed to 40° C. A 7.49 g shot of a 0.06 M solution of sec-butyllithium in cyclohexane was then rapidly added to the reactor via cannula, causing the reactor contents to turn yellow-orange. The reactor contents were allowed to stir for 30 minutes. A small portion of the reactor contents was then withdrawn from the reactor into a small round bottomed flask containing anhydrous methanol for gel permeation chromatography analysis of the polystyrene block formed. Then 22.39 g of a 21 wt % solution of freshly sublimed hexamethylcyclotrisiloxane in cyclohexane was transferred to the reactor. The reactor contents were allowed to react for 20 hours. Then dry tetrahydrofuran (93 mL) was added to the reactor and the reaction was allowed to proceed for 7 hours. Chlorotrimethylsilane (1 mL) was then added to the reactor to quench the reaction. The product was isolated by precipitating into 1 L of methanol and filtering. After washing with additional methanol, the polymer was redissolved in 150 mL of methylene chloride, washed twice with deionized water and then reprecipitated into 1 L of methanol. The polymer was then filtered and dried overnight in a vacuum oven at 60° C., yielding 19.7 g. The poly(styrene)-b-poly(dimethyl siloxane) block copolymer (“BCP1”) product exhibited a number average molecular weight, M_(N), of 40 kg/mol; a polydispersity, PD, of 1.11 and a 22.2 wt % PDMS content (as determined by ¹H NMR).

Example 3 Preparation of PS-b-PDMS Diblock Copolymer

Into a 500 mL round bottom reactor under an argon atmosphere was added cyclohexane (90 mL) and styrene (18.4 g). A 0.5 mL shot of a 1.4 M solution of sec-butyllithium in cyclohexane was then rapidly added to the reactor via cannula, causing the reactor contents to turn yellow-orange. The reactor contents were allowed to stir for 30 minutes. A small portion of the reactor contents was then withdrawn from the reactor into a small round bottomed flask containing anhydrous methanol for gel permeation chromatography analysis of the polystyrene block formed. Next 2,2,5,5-tetramethyldisilafuran (337 mg) was added to the reactor. Slowly the orange color began to fade, and after 1 hour the contents of the reactor were slightly yellow in color. Then 10.1 g of freshly sublimed hexamethylcyclotrisiloxane was transferred to the reactor. The reactor contents were allowed to react for 1.5 hours until the reactor contents were colorless. Then dry tetrahydrofuran (90 mL) was added to the reactor and the reaction was allowed to proceed for 3.25 hours. Chlorotrimethylsilane (1 mL) was then added to the reactor to quench the reaction. The product was isolated by precipitating into 500 mL of methanol and filtering. After washing with additional methanol, the polymer was redissolved in 150 mL of methylene chloride, washed three times with deionized water and then reprecipitated into 500 mL of methanol. The polymer was then filtered and dried overnight in a vacuum oven at 70° C., yielding 22.1 g. The poly(styrene)-b-poly(dimethyl siloxane) block copolymer (“BCP2”) product exhibited a number average molecular weight, M_(N), of 35.8 kg/mol; a polydispersity, PD, of 1.01 and a 25 wt % PDMS content (as determined by ¹H NMR).

Example 4 Preparation PS-b-PDMS Diblock Copolymer

Into a 500 mL round bottom reactor under an argon atmosphere was added cyclohexane (90 mL) and styrene (17.1 g). A 0.7 mL shot of a 1.4 M solution of sec-butyllithium in cyclohexane was then rapidly added to the reactor via cannula, causing the reactor contents to turn yellow-orange. The reactor contents were allowed to stir for 30 minutes. A small portion of the reactor contents was then withdrawn from the reactor into a small round bottomed flask containing anhydrous methanol for gel permeation chromatography analysis of the polystyrene block formed. Next 2,2,5,5-tetramethyldisilafuran (472 mg) was added to the reactor. Slowly the orange color began to fade, and after 1 hour the contents of the reactor were slightly yellow in color. Then 10.5 g of freshly sublimed hexamethylcyclotrisiloxane was transferred to the reactor. The reactor contents were allowed to react for 1.5 hours until the reactor contents were colorless. Then dry tetrahydrofuran (90 mL) was added to the reactor and the reaction was allowed to proceed for 3.25 hours. Chlorotrimethylsilane (1 mL) was then added to the reactor to quench the reaction. The product was isolated by precipitating into 500 mL of methanol and filtering. After washing with additional methanol, the polymer was redissolved in 150 mL of methylene chloride, washed three times with deionized water and then reprecipitated into 500 mL of methanol. The polymer was then filtered and dried overnight in a vacuum oven at 70° C., yielding 20.5 g. The poly(styrene)-b-poly(dimethyl siloxane) block copolymer (“BCP3”) product exhibited a number average molecular weight, M_(N), of 24.4 kg/mol; a polydispersity, PD, of 1.0 and a 28 wt % PDMS content (as determined by ¹H NMR).

Example 5 Preparation PS-b-PDMS Diblock Copolymer

Into a 500 mL round bottom reactor under an argon atmosphere was added cyclohexane (91 g) and styrene (19.41 g). The contents of the reactor were warmed to 40° C. using a warm water bath. A 2.31 g shot of a 0.6 M solution of sec-butyllithium in cyclohexane was then rapidly added to the reactor via cannula, causing the reactor contents to turn yellow. The reactor contents were allowed to stir for 40 minutes. A small portion of the reactor contents was then withdrawn from the reactor into a small round bottomed flask containing anhydrous methanol for gel permeation chromatography analysis of the polystyrene block formed. Then 26.31 g of freshly sublimed hexamethylcyclotrisiloxane was transferred to the reactor. The reactor contents were allowed to react for 6 hours until the reactor contents were colorless. Then dry tetrahydrofuran (135 mL) was added to the reactor and the reaction was allowed to proceed for 16 hours. Chlorotrimethylsilane (1 mL) was then added to the reactor to quench the reaction. The product was isolated by precipitating into 1 L of methanol and filtering. After washing with additional methanol, the polymer was redissolved in 150 mL of methylene chloride, washed twice with deionized water and then reprecipitated into 1 L of methanol. The polymer was then filtered and dried overnight in a vacuum oven at 60° C. The poly(styrene)-b-poly(dimethyl siloxane) block copolymer (“BCP4”) product exhibited a number average molecular weight, M_(N), of 14.2 kg/mol; a polydispersity, PD, of 1.1 and a 25 wt % PDMS content (as determined by ¹H NMR).

Example 6 PS-b-PDMS Diblock Copolymer Filtering

Each of the PS-b-PDMS diblock copolymers prepared according to Example 2-5 was added to propylene glycol methyl ether acetate (PGMEA) (Dowanol® PMA from The Dow Chemical Company) to form a 1.6 wt % solution. The 1.6 wt % solutions formed were then separately hand filtered through a 0.2 μm Whatman syringe filter. The product filtrate material was collected for further use.

Example 7 Preparation of Diblock Copolymer Blend

The product filtrate of Example 6 obtained from a PS-b-PDMS diblock copolymer prepared according to Example 2 (BCP1) and the product filtrate of Example 6 obtained from a PS-b-PDMS diblock copolymer prepared according to Example 5 (BCP4) were combined to form a diblock copolymer blend (Blend1) having 55 wt % of BCP1 (M_(N-BCP1) is 40 kg/mol) and 45 wt % BCP4 (M_(N-BCP4) is 14.2 kg/mol). Accordingly, the average molecular weight of Blend1 is 28.39 kg/mol.

Example 8 Preparation of Diblock Copolymer Blend

The product filtrate of Example 6 obtained from a PS-b-PDMS diblock copolymer prepared according to Example 3 (BCP2) and the product filtrate of Example 6 obtained from a PS-b-PDMS diblock copolymer prepared according to Example 5 (BCP4) were combined to form a diblock copolymer blend (Blend2) having 60 wt % of BCP2 (M_(N-BCP2) is 35.8 kg/mol) and 40 wt % BCP4 (M_(N-BCP4) is 14.2 kg/mol). Accordingly, the average molecular weight of Blend2 is 27.16 kg/mol.

Example 9 Substrate Preparation

The surface of a silicon substrate having a native oxide layer was modified by spin coating thereon a 1.5 wt % (solids) solution of the hydroxyl-terminated polystyrene bush prepared according to Example 1 in toluene at 3,000 rpm for 1 minute. The substrate was then placed on a hotplate set at 150° C. for 1 minute. The substrate was then placed on a hot plate set at 250° C. under a nitrogen atmosphere for 20 minutes to anneal the deposited brush layer. The substrate was then rinsed with toluene to wash away any unattached polymer by first soaking the substrate in toluene for 1 minute and then spin drying at 3,000 rpm for 1 minute. The substrate was then baked on a hotplate set at 110° C. for one minute.

Comparative Example F1 and Example 10 Film Annealing

A PS-b-PDMS block copolymer prepared according to Example 2 (BCP1) was dissolved in propylene glycol methyl ether acetate (Dowanol® PMA from the Dow Chemical Company) to form a 1.8 wt % solution. The solution was then hand filtered using a 0.2 μm Whatman syringe filter. The filtered solution was then spin coated at 3,061 rpm onto two poly(styrene) brushed substrates prepared according to Example 9 to obtain a deposited film thickness of 38.3 nm. The substrates were then baked on a hotplate set at 150° C. for 1 minute. The deposited films were then annealed by placing one substrate on a hotplate set at 180° C. for one hour under a nitrogen atmosphere containing <6 ppm oxygen (i.e., Comparative Example F1); and placing the other substrate on a hotplate set at 290° C. for one hour under a nitrogen atmosphere containing <6 ppm oxygen (i.e., Example 10).

A surface wetting layer of PDMS formed on both annealed films at the atmosphere film interface. The annealed films were then treated using two consecutive reactive ion etching (RIE) steps using a PlasmaTherm 790i RIE to reveal the block copolymer morphology of the deposited BCP1 films. First, a short CF₄ plasma (10 mT, 50 W) RIE treatment (8 seconds post plasma stabilization) was used to punch through the surface wetting layer of PDMS. Then, an O₂ plasma RIE treatment (25 seconds post plasma stabilization) was employed to remove the polystyrene and convert the PDMS to SiO_(x).

The plasma treated film was then examined by Scanning Electron Microscopy. The test samples were mounted on the SEM stage using double sided carbon tape and cleaned by blowing nitrogen prior to analysis. An image of each test sample was collected at 50,000× magnification and working distances between 4 and 8. Top down SEM image of the product films are shown in FIGS. 1 and 2, for Comparative Example F1 and Example 10, respectively.

At equilibrium, the morphology of the BCP1 film is expected by theory to be surface parallel cylinders given the preference for the poly(styrene) in BCP1 film to the poly(styrene) in the brush layer on the substrate. As seen from the SEM image in FIG. 1, use of a conventional anneal temperature resulted in a film exhibiting a micellar morphology with a very small fraction of short parallel cylinders. This result comports with the conventional wisdom that thermal annealing does not work for PS-b-PDMS films.

As seen from the SEM image in FIG. 2, however, the thermal annealing process of the present invention results in fingerprint morphology consistent with parallel cylinders of PDMS, which is the theoretically expected equilibrium morphology for the BCP1 film.

Comparative Example F2 and Example 11 Film Annealing

A PS-b-PDMS block copolymer prepared according to Example 6 (BCP5) was dissolved in propylene glycol methyl ether acetate (Dowanol® PMA from the Dow Chemical Company) to form a 2 wt % solution. The solution was then hand filtered using a 0.2 μm Whatman syringe filter. The filtered solution was then spin coated at 2,500 rpm onto two poly(styrene) brushed substrates prepared according to Example 9 to obtain a deposited film thickness of 40 nm. The substrates were then baked on a hotplate set at 150° C. for 1 minute. The deposited films were then annealed by placing one substrate on a hotplate set at 340° C. for one hour under a nitrogen atmosphere containing 8 ppm oxygen (i.e., Comparative Example F2); and placing the other substrate on a hotplate set at 340° C. for one hour under a nitrogen atmosphere containing 4 ppm oxygen (i.e., Example 11).

A surface wetting layer of PDMS formed on both annealed films at the atmosphere film interface. The annealed films were then treated using two consecutive reactive ion etching (RIE) steps using a PlasmaTherm 790i RIE to reveal the block copolymer morphology of the deposited BCP1 films. First, a short CF₄ plasma (10 mT, 50 W) RIE treatment (8 seconds post plasma stabilization) was used to punch through the surface wetting layer of PDMS. Then, an O₂ plasma RIE treatment (25 seconds post plasma stabilization) was employed to remove the polystyrene and convert the PDMS to SiO_(x).

The plasma treated film was then examined by Scanning Electron Microscopy. The test samples were mounted on the SEM stage using double sided carbon tape and cleaned by blowing nitrogen prior to analysis. An image of each test sample was collected at 50,000× magnification and working distances between 4 and 8. Top down SEM image of the product films are shown in FIGS. 3 and 4, for Comparative Example F2 and Example 11, respectively.

At equilibrium, the morphology of the BCP5 film is expected by theory to be surface parallel cylinders given the preference for the poly(styrene) in the BCP5 film to the poly(styrene) in the brush layer on the substrate. As seen from the SEM image in FIG. 3, as the oxygen level in the atmosphere above the annealing film increases to 8 ppm, the resulting morphology of the deposited BCP5 film was a mixture of parallel cylinders and perpendicular cylinders or spheres. Only a fraction of the cylinders oriented parallel to the substrates surface as would be expected from theory. Also, the pitch exhibited by the film was 30 nm.

As seen from the SEM image in FIG. 4, however, the thermal annealing process of the present invention results in the majority of the PDMS cylinders being oriented parallel to the substrate surface to give a fingerprint pattern characteristic of the expected structure along with an exhibited pitch of 27 nm.

Example 12 Film Preparation

A PS-b-PDMS block copolymer prepared according to Example 4 (BCP3) was dissolved in propylene glycol methyl ether acetate (Dowanol® PMA from the Dow Chemical Company) to form a spinning solution. The spinning solution was then hand filtered using a 0.2 μm Whatman syringe filter. The filtered solution was then spin coated onto a poly(styrene) brushed substrate prepared according to Example 9 to obtain a deposited film thickness of 30-35 nm. The substrate was then baked on a hotplate set at 150° C. for 1 minute. The deposited film was then annealed by placing the substrate on a hotplate set at 340° C. for two minutes under a nitrogen atmosphere containing <6 ppm oxygen.

The annealed film was then treated using two consecutive reactive ion etching (RIE) steps using a PlasmaTherm 790i RIE to reveal the block copolymer morphology of the deposited BCP3 film. First, a short CF₄ plasma (10 mT, 50 W) RIE treatment (8 seconds post plasma stabilization) was used to punch through the surface wetting layer of PDMS. Then, an O₂ plasma RIE treatment (25 seconds post plasma stabilization) was employed to remove the polystyrene and convert the PDMS to SiO_(x).

Example 13 Film Preparation

A PS-b-PDMS diblock copolymer blend prepared according to Example 7 (Blend1) was dissolved in propylene glycol methyl ether acetate (Dowanol® PMA from the Dow Chemical Company) to form a spinning solution. The spinning solution was then hand filtered using a 0.2 μm Whatman syringe filter. The filtered solution was then spin coated onto a poly(styrene) brushed substrate prepared according to Example 9 to obtain a deposited film thickness of 30-35 nm. The substrate was then baked on a hotplate set at 150° C. for 1 minute. The deposited film was then annealed by placing the substrate on a hotplate set at 340° C. for two minutes under a nitrogen atmosphere containing <6 ppm oxygen.

The annealed film was then treated using two consecutive reactive ion etching (RIE) steps using a PlasmaTherm 790i RIE to reveal the block copolymer morphology of the deposited BCP3 film. First, a short CF₄ plasma (10 mT, 50 W) RIE treatment (8 seconds post plasma stabilization) was used to punch through the surface wetting layer of PDMS. Then, an O₂ plasma RIE treatment (25 seconds post plasma stabilization) was employed to remove the polystyrene and convert the PDMS to SiO_(x).

Example 14 Film Preparation

A PS-b-PDMS diblock copolymer blend prepared according to Example 8 (Blend 2) was dissolved in propylene glycol methyl ether acetate (Dowanol® PMA from the Dow Chemical Company) to form a spinning solution. The spinning solution was then hand filtered using a 0.2 μm Whatman syringe filter. The filtered solution was then spin coated onto a poly(styrene) brushed substrate prepared according to Example 9 to obtain a deposited film thickness of 30-35 nm. The substrate was then baked on a hotplate set at 150° C. for 1 minute. The deposited film was then annealed by placing the substrate on a hotplate set at 340° C. for two minutes under a nitrogen atmosphere containing <6 ppm oxygen.

The annealed film was then treated using two consecutive reactive ion etching (RIE) steps using a PlasmaTherm 790i RIE to reveal the block copolymer morphology of the deposited BCP3 film. First, a short CF₄ plasma (10 mT, 50 W) RIE treatment (8 seconds post plasma stabilization) was used to punch through the surface wetting layer of PDMS. Then, an O₂ plasma RIE treatment (25 seconds post plasma stabilization) was employed to remove the polystyrene and convert the PDMS to SiO_(x).

Example 15 Film Comparison

The plasma treated films of Examples 12-14 were then examined by Scanning Electron Microscopy. Analysis of the plasma treated films showed that the blends (i.e., Blend1 & Blend2) exhibited longer, straighter cylinders than the comparable average molecular weight neat PS-b-PDMS diblock copolymer, BCP3; thus demonstrating that the blended films exhibit a faster annealing behavior, compared to an unblended diblock copolymer of comparable average molecular weight. 

We claim:
 1. A method for processing a substrate, comprising: providing a substrate having a surface; providing a copolymer composition, comprising a poly(styrene)-b-poly(dimethylsiloxane) block copolymer component, wherein the number average molecular weight of the poly(styrene)-b-poly(dimethylsiloxane) block copolymer component is 25 to 1,000 kg/mol; applying a film of the copolymer composition to the surface of the substrate; optionally, baking the film; heating the film at 275 to 350° C. under a gaseous atmosphere having an oxygen concentration of ≦7.5 ppm for a period of 1 second to 4 hours; and, treating the annealed film to remove the poly(styrene) from the annealed film and to convert the poly(dimethylsiloxane) in the annealed film to SiO_(x).
 2. The method of claim 1, wherein the poly(styrene)-b-poly(dimethylsiloxane) block copolymer component provided is a single poly(styrene)-b-poly(dimethylsiloxane) diblock copolymer having a number average molecular weight, M_(N), of 25 to 1,000 kg/mol; a polydispersity, PD, of 1 to 3; and a poly(dimethylsiloxane) weight fraction, Wf_(PDMS), of 0.19 to 0.33.
 3. The method of claim 2, wherein the copolymer composition provided further comprises a solvent; wherein the solvent is selected from the group consisting of propylene glycol monomethyl ether acetate (PGMEA), ethoxyethyl propionate, anisole, ethyl lactate, 2-heptanone, cyclohexanone, amyl acetate, γ-butyrolactone (GBL), n-methylpyrrolidone (NMP) and toluene.
 4. The method of claim 2, wherein the copolymer composition provided further comprises an additive; wherein the additive is selected from the group consisting of additional polymers (including homopolymers and random copolymers); surfactants; antioxidants; photoacid generators; thermal acid generators; quenchers; hardeners; adhesion promoters; dissolution rate modifiers; photocuring agents; photosensitizers; acid amplifiers; plasticizers; orientation control agents and cross linking agents.
 5. The method of claim 1, wherein the poly(styrene)-b-poly(dimethylsiloxane) block copolymer component is a blend of at least two different poly(styrene)-b-poly(dimethylsiloxane) block copolymers; wherein the at least two different poly(styrene)-b-poly(dimethylsiloxane) block copolymers are selected from the group of poly(styrene)-b-poly(dimethylsiloxane) block copolymers having a number average molecular weight, M_(N), of 1 to 1,000 kg/mol and a polydispersity, PD, of 1 to 3; and, wherein the blend exhibits a blend number average molecular weight, M_(N-Blend), of 25 to 1,000 kg/mol.
 6. The method of claim 5, wherein the blend exhibits a blend poly(dimethylsiloxane) weight fraction, Wf_(PDMS-Blend), of 0.19 to 0.33.
 7. The method of claim 6, wherein the copolymer composition provided further comprises a solvent; wherein the solvent is selected from the group consisting of propylene glycol monomethyl ether acetate (PGMEA), ethoxyethyl propionate, anisole, ethyl lactate, 2-heptanone, cyclohexanone, amyl acetate, γ-butyrolactone (GBL), n-methylpyrrolidone (NMP) and toluene.
 8. The method of claim 6, wherein the copolymer composition provided further comprises a solvent; wherein the solvent is selected from the group consisting of propylene glycol monomethyl ether acetate (PGMEA) and toluene.
 9. The method of claim 6, wherein the copolymer composition provided further comprises an additive; wherein the additive is selected from the group consisting of additional polymers (including homopolymers and random copolymers); surfactants; antioxidants; photoacid generators; thermal acid generators; quenchers; hardeners; adhesion promoters; dissolution rate modifiers; photocuring agents; photosensitizers; acid amplifiers; plasticizers; orientation control agents and cross linking agents.
 10. A substrate processed according to the method of claim
 1. 